氰酸酯改性环氧树脂耐热性研究

采用热变形仪和红外光谱研究了氰酸酯树脂(CE)改性环氧树脂(EP)体系的4种不同配比和不同固化温度对产物的耐热性的影响。结果表明:加入CE树脂能显著提高EP的耐热性,但固化温度对CE树脂含量不同体系的热变形温度(HDT)影响程度有明显差别。CE/EP体系中EP过量时,提高固化温度,产物的HDT显著提高,在230℃以上固化反应才能完成;两者相当或CE过量时,固化温度在180～200℃时产物的HDT最高,提高固化温度,产物的HDT反而下降。CE含量不同时,反应生成的产物各异,这是造成固化物HDT差异的根本原因。     

环氧及酚醛树脂增韧改性氰酸酯树脂研究

用环氧树脂(EP)及酚醛树脂(PF)对氰酸酯树脂(CE)进行增韧改性,对改性CE的凝胶时间和DSC曲线进行研究并确定了改性CE的固化工艺。红外光谱分析表明改性CE固化时形成了柔韧性结构。研究了改性CE的力学性能、热性能、电性能及微观形态,发现EP的加入可增加CE的柔韧性,PF的加入可使CE的热稳定性损失减小。当CE/EP/PF的质量比为70/15/15时改性CE的弯曲强度和冲击强度分别从改性前的123.6 MPa、5.2 kJ/m2提高到134.5 MPa、16.7 kJ/m2,耐热性及电性能改变不大。     

纳米SiO_2改性EP/BMI/CE树脂体系固化动力学研究

采用非等温差示扫描量热(DSC)法对纳米二氧化硅/环氧树脂/双马来酰亚胺/氰酸酯(nano-SiO2/EP/BMI/CE)树脂进行了固化反应动力学和固化工艺研究。通过Kissinger法和Ozawa法求得了nano-SiO2/EP/BMI/CE树脂体系固化反应动力学的表观活化能。结果表明:改性CE树脂体系的固化工艺参数为凝胶温度112℃、固化温度195℃及后处理温度213℃,进而确定了改性CE树脂体系的最佳固化工艺条件为"150℃/3 h→180℃/3 h→200℃/2 h";改性CE树脂体系的平均表观活化能为59.90 kJ/mol。     

氰酸酯树脂／环氧树脂共混物的结构与性能研究

采用原位红外光谱法确定了氰酸酯树脂(CE)/环氧树脂(EP)体系的共固化反应机理,研究了非催化条件下EP含量对产物结构的影响,并且研究了不同配比的CE/EP共混物的结构与性能之间的关系.研究表明,随EP含量的增加,产物中恶唑烷酮含量增加,相应浇注体的冲击性能有明显提高,但弯曲性能略有下降;凝胶点测试表明,EP可以有效促进CE的固化反应.     

氰酸酯树脂/环氧树脂共混物的化学和性能

氰酸酯 (CE)树脂 /环氧 (EP)树脂是一类具有特殊反应活性的树脂混合物。CE/EP的固化物由于自身独特的结构特征 ,是一类性能优异的树脂共混物。重点介绍了CE/EP的反应机理和主要性能。     

CE/EP/纳米SiC复合材料研究

采用纳米SiC和环氧树脂(EP)对双酚A型氰酸酯树脂(CE)进行改性。研究了不同含量的纳米SiC对CE/EP/纳米SiC复合体系反应性及CE/EP/纳米SiC复合材料力学性能的影响,采用透射电子显微镜表征了材料的微观形貌,利用差示扫描量热法研究了固化树脂的热性能。结果表明,纳米SiC对CE/EP/纳米SiC复合体系具有明显的催化作用,并且能使复合材料的冲击强度提高123.62%,弯曲强度提高140.29%,有效发挥其增强增韧作用,还能很好地保持复合材料的耐热性能。     

环氧树脂改性双马来酰亚胺/氰酸酯树脂固化工艺研究

采用差示扫描量热(DSC)法和红外光谱(FT-IR)法对缩水甘油胺型环氧树脂(AG-80)与脂环族缩水甘油酯型环氧树脂(TDE-85)共同改性双马来酰亚胺(BMI)/氰酸酯树脂(CE)的固化反应历程进行了研究,并按照Kissinger和Crane法计算出该改性树脂体系固化反应的动力学参数。结果表明:改性树脂体系的固化反应表观活化能为68.11 kJ/mol,固化反应级数为0.860(接近于1级反应);环氧树脂(EP)可促进CE固化,当固化工艺条件为"150℃/3 h→180℃/2 h"时,改性树脂体系可以固化完全。     

环氧树脂/氰酸酯树脂体系的改性研究

为增加环氧树脂/氰酸酯树脂体系(EP/CE)的韧性,向EP/CE树脂体系中引入第三组分——双酚A(BPA)。采用傅里叶转换红外光谱、差式扫描量热仪研究了BPA对EP/CE固化温度与固化机理的影响,测定了固化物的力学性能和耐湿热性。结果表明,BPA的加入改变了EP/CE树脂体系固化历程,引起EP/CE树脂体系固化温度明显下降。BPA在EP/CE树脂体系内可形成大量的—C—O—C—键,与EP/CE树脂体系形成互穿网络,提高了EP/CE的韧性。随着体系中BPA含量的增加,其力学性能提高,吸水率有所下降。当CE∶EP∶BPA质量比为7∶3∶0.75时,其拉伸强度提高27.3%,冲击强度提高34.7%,吸湿率降为1.2%。     

环氧树脂/氰酸酯树脂共混物的热性能与吸湿性能

研究了氰酸酯树脂(CE)改性环氧树脂(EP)的热性能和吸湿性能.结果表明,一定量的CE可以显著提高EP/CE共混物的耐热性,同时其吸水率远低于常见的EP体系.当加入质量分数50%的CE时,共混物的玻璃化转变温度(Tg)提高至210℃,沸水浸泡48 h后共混物的吸水率仅为1.37%,扩大了EP的应用领域.     

热固性树脂/碳纳米管复合材料的研究进展

介绍了碳纳米管(CNTs)在改性环氧树脂(EP)、酚醛树脂(PF)、双马来酰亚胺树脂(BMI)以及氰酸酯树脂(CE)等热固性树脂方面的应用,综述了EP/CNTs、PF/CNTs、BMI/CNTs、CE/CNTs复合材料的近期研究进展,详细叙述了CNTs对热固性树脂的力学性能、热性能、摩擦性能的改善情况,结合扫描电镜分析结果研究了CNTs在EP和BMI中的分散情况,并指出了热固性树脂/CNTs复合材料存在的问题和应用前景。     

Effect of cyanate ester on the cure behavior and thermal stability of epoxy resin

Epoxy resin (diglycidyl ether of bisphenol A, DGEBA)/cyanate ester mixtures were cured with a curing agent, 4,4′-diaminodiphenylsulfone, and the effect of cyanate ester resin on the cure behavior and thermal stability in the epoxy resin was investigated with a Fourier transform infrared spectrometer, a rheometer, a dynamic mechanical analyzer, and a thermogravimetric analyzer. Cure reactions in the epoxy/cyanate ester mixture were faster than that of the neat epoxy system. The cure reaction was accelerated by increasing the cyanate ester resin component. Glass transition temperature and thermal stability in the cured resins were increased with increasing cyanate ester resin component. This may be caused by the increase of crosslinking density due to the polycyclotrimerization of the cyanate ester monomer to form triazine rings and the reaction of cyanate ester resin with the epoxy network. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 85–90, 1997     

The effect of different metallic catalysts on the coreaction of cyanate/epoxy

The curing reaction between the diepoxy and dicyanate mixed resins in the presence of three different catalysts Cu(AcAc)₂, manganese octoate, and copper octoate was investigated. The thermal behavior was monitored using differential scanning calorimeter; the transformations of structures during the isothermal and heating process were explored by Fourier transform infrared spectroscopy; the changes of the carbonic‐framework of polymer and intermediate products were analyzed by nuclear magnetic resonance. Conclusions can be drawn as follows: Similar to noncatalyzed system, the overall reaction still occurs in two steps: cyclotrimerization of cyanate ester to produce triazine rings, coupled with the formation of some secondary intermediate products, and coreaction of epoxy and triazine rings to form oxazolidinone rings at high temperature. The catalysts can accelerate the curing process and decrease the curing temperature as well as gel time, and manganese octoate presents the best effect on curing rate. But the mechanisms and the structures of intermediate products of metallic‐catalyzed epoxy/cyanate are not changed by the addition of catalysts. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2293–2302, 2006     

低溴环氧/氰酸酯树脂共固化反应及其层压板性能的研究

用差示扫描量热仪(DSC)、傅立叶交换红外光谱(FT-IR)对不同配比的低溴环氧／氰酸酯树脂的共固化反应机理以及固化物的结构特征进行了研究,同时测定和讨论了其层压板的耐热性和介电性能等。研究结果表明,在低溴环氧／氰酸酯树脂的固化体系中,氰酸酯和环氧树脂通过两种途径反应最终生成噁唑烷酮结构：固化反应温度与体系的组成有关,体系中低溴环氧树脂减少固化反应温度降低：加入催化剂能明显促进体系共固化反应,同时也降低了层压板的耐热性和介电性能。在性能方面,低溴环氧树脂中加入氰酸酯使共固化物耐热性增加、Tg升高,但氰酸酯用量增加到一定范围后,低溴环氧树脂／氰酸酯配比对Tg影响不大;低溴环氧树脂／氰酸酯层压板的耐热性和介电性能在一定实验范围内随着氰酸酯用量的增加明显提高。     

双酚A二氰酸酯/环氧树脂固化共混物结构的红外光谱研究

通过熔融共混制备了双酚A二氰酸酯/双酚A二缩水甘油醚环氧树脂、双酚A二氰酸酯/酚醛环氧树脂两种共混物。用红外光谱研究了组分比对两类共混物各种基团相对含量的影响。结果表明,随着共混物中环氧量的增加,芳醚的吸收会由于共聚产物的增加而出现蓝移,酚醛环氧树脂中的酚羟基能影响共聚产物的生成;环氧量较大的氰酸酯/酚醛环氧村脂共混物生成了相当含量的酚-氰酸酯加成物,这使得共聚产物相对含量的计算变得困难。     

氰酸酯改性环氧树脂的研究进展

氰酸酯改性环氧树脂是一种新型的具有广阔应用前景的高性能复合基体材料。综述氰酸酯改性环氧树脂的反应历程、反应条件对固化反应产物的影响及在工业领域中的应用。     

环氧改性氰酸酯树脂的研究

综述采用环氧树脂增韧改性氰酸酯树脂的共聚反应机理、固化催化体系，以及环氧树脂／氰酸酯树脂固化体系的性能和复合材料的性能。环氧树脂与氰酸酯树脂反应生成恶唑啉酮五元环，降低了氰酸酯树脂的交联密度，使韧性提高；催化剂可以明显提高共聚反应速度，改变产物含量；改性后的氰酸酯树脂具有优良的综合力学性能和成型工艺性，且介电性能及耐热／湿热性能无较大损失。     

Curing behavior and network formation of cyanate ester resin/polyethylene glycol

The mechanism and kinetics of the curing reaction of cyanate ester (CE) resin modified with polyethylene glycol were investigated by means of differential scanning calorimetry (DSC) and Fourier‐transform infrared spectroscopy (FTIR). The relationship of heat flow versus conversion rate was used to evaluate the effects of polyethylene glycol (PEG) on the curing reaction of CE. DSC results showed that the addition of PEG decreased the curing temperature of CE effectively when its content was less than 20 wt %. The curing behavior of CE/PEG still complies with the self‐catalytic kinetic model proposed by Kamal. The effects of PEG content on the kinetics parameters and conversion rate of the curing reaction were discussed. FTIR results indicated that the –OH groups in PEG participated in the polymeric reaction of CE and formed –O–C (=NH) –O– structure through block copolymerization, which extended the chain length between triazine rings and reduced the density of triazine rings. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41841.     

Properties of cyanate ester-cured epoxy/polyphenylene oxide blends as a matrix material for Kevlar fiber composites

Epoxy/polyphenylene oxide (PPO) blends were cured with multifunctional cyanate ester resin. The effects of the PPO content on the cure behavior in the cyanate ester-cured epoxy were investigated with Fourier transform infrared spectroscopy (FTIR). The cure reaction in the epoxy/PPO blends was faster than that of the neat epoxy system. FTIR analysis revealed that the cyanate functional group reactions were accelerated by adding PPO and that several co-reactions had occurred, such as cyanate-hydroxyl addition and epoxy-cyanate addition. This was caused by the reaction of cyanate ester with the PPO phenolic end-group and water yielding imidocarbonate and carbamate intermediate which can react with cyanate ester to form cyanurate. Then the cyanurate can react further with the epoxy resin. Thermal mechanical analysis showed that the thermal stability of the epoxy/PPO blends is improved by adding PPO. The morphology of the fiber-rich areas in the composite is different from that of the epoxy/PPO blend without Kevlar fiber. In the pure polymer blends with high PPO content (30 and 50 phr), phase separation and phase inversion were observed. In the composites, the majority of the epoxy resin migrates to the polar fiber surface, resulting in epoxy-coated fibers. So the interfacial shear strength (IFSS) between Kevlar fiber and the epoxy/PPO blends is almost the same as that between Kevlar fiber and neat epoxy. The presence of PPO does not affect the interfacial property in the epoxy/PPO/fiber composite. So the interlaminar shear strength (ILSS) increase with the PPO content is due to an increase in the composite's ductility or toughness.     

环氧树脂含量对氰酸酯热学性能的影响研究

采用示差扫描量热法(DSC)和热失重分析法(TGA)研究了环氧树脂含量对氰酸酯树脂固化反应特性、热稳定性以及热膨胀系数的影响。结果表明,环氧树脂的加入可有效降低改性体系的固化反应活化能,同时体系的热稳定性和尺寸稳定性有不同程度的削弱。当环氧树脂质量分数达到20%时,改性体系的表观活化能为65.4 kJ/mol,耐热温度指数为174℃,较纯氰酸酯树脂分别降低了25.8%和21.4%。当环氧树脂质量分数达到50%时,改性体系的热膨胀系数为65.3 922×10-6/℃(25～150℃),较纯氰酸酯树脂提高了8.13%。     

酚醛型环氧树脂改性氰酸酯复合材料性能的研究

通过DSC分析,粘度、介电性能、力学性能及耐油性测试对酚醛型环氧树脂改性氰酸酯树脂复合材料的性能进行了研究。结果表明,改性氰酸酯树体系在70～160℃具有较低的粘度,理想工艺是在125～130℃下30～45min后开始加压;改性氰酸酯树脂表观活化能和反应级数分别为60.81kJ/mol和0.8846。改性氰酸酯复合材料具有良好的力学性能、介电性能和耐油性能。